Welcome to this virtual special issue, which focuses on supramolecular/macrocyclic Chemistry. The beginnings of supramolecular chemistry can be traced back to 1967 with the identification of crown ethers by Pedersen [...Welcome to this virtual special issue, which focuses on supramolecular/macrocyclic Chemistry. The beginnings of supramolecular chemistry can be traced back to 1967 with the identification of crown ethers by Pedersen [1], and being acknowledgement by the 1987 Nobel Prize to Lehn, Cram, and Pedersen for their leading discoveries in the host-guest systems [2]. Since these展开更多
The construction of an unprecedented intertwined spiral solvent channel is driven by weak C–Cl…O and C–H…N interactions based on extraordinary parallel spirals which were structured from supramolecular synthon mac...The construction of an unprecedented intertwined spiral solvent channel is driven by weak C–Cl…O and C–H…N interactions based on extraordinary parallel spirals which were structured from supramolecular synthon macrocycle 1（C44H44N4O4） with a propargylamine backbone. The product is characterized by ^1H NMR, ^13C NMR, IR and HRMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 28.922（3）, b = 8.5069（9）, c = 21.687（2）A^°, β = 130.6320（10）°, V = 4049.4（7） A^°3 and Z = 8. A total of 11874 reflections were collected, of which 4942 were independent（Rint = 0.0590） and 2937 were observed with I 〉 2σ（I）. The final full-matrix least-squares refinement gave R（I 〉 2s（I）） = 0.069 and w R = 0.167, S = 1.05,（Δρ）max = 0.20 and（Δρ）min =-0.22 e·A^1-3. The fluorescence of the product is discussed.展开更多
Enhancing the proton conductivity of proton exchange membranes(PEMs)is essential to expand the applications of proton exchange membrane fuel cells(PEMFCs).Inspired by the proton conduction mechanism of bacteriorhodops...Enhancing the proton conductivity of proton exchange membranes(PEMs)is essential to expand the applications of proton exchange membrane fuel cells(PEMFCs).Inspired by the proton conduction mechanism of bacteriorhodopsin,cucurbit[n]urils(CB[n],where n is the number of glycoluril units,n=6,7,or 8)are introduced into sulfonated poly(ether ether ketone)(SPEEK)matrix to fabricate hybrid PEMs,employing a nature-inspired chemical engineering(NICE)methodology.The carbonyl groups of CB[n]act as proton-conducting sites,while the host–guest interaction between CB[n]and water molecules offers extra protonconducting pathways.Additionally,the molecular size of CB[n]aids in their dispersion within the SPEEK matrix,effectively bridging the unconnected proton-conducting sulfonic group domains within the SPEEK membrane.Consequently,all hybrid membranes exhibit significantly enhanced proton conductivity.Notably,the SPEEK membrane incorporating 1 wt.%CB[8](CB[8]/SPEEK-1%)demonstrates the highest proton conductivity of 198.0 mS·cm^(−1) at 60°C and 100%relative humidity(RH),which is 228%greater than that of the pure SPEEK membrane under the same conditions.Moreover,hybrid membranes exhibit superior fuel cell performance.The CB[8]/SPEEK-1%membrane achieves a maximum power density of 214 mW·cm^(−2),representing a 140%improvement over the pure SPEEK membrane(89 mW·cm^(−2))at 50°C and 100%RH.These findings serve as a foundation for constructing continuous proton-conducting pathways within membranes by utilizing supramolecular macrocycles as fuel cell electrolytes and in other applications.展开更多
A series of macrocycles, including crown ethers, cyclodextrins, calixarenes, pillararenes and cucurbiturils, are well known to be able to associate various organic/inorganic/biological guest molecules and ions in thei...A series of macrocycles, including crown ethers, cyclodextrins, calixarenes, pillararenes and cucurbiturils, are well known to be able to associate various organic/inorganic/biological guest molecules and ions in their well-defined cyclic cavities to form stable host-guest complexes and supramolecular systems through the cooperative contributions of various non-covalent interactions.When one or more functional groups are attached to the cavity of macrocycles or guest molecules, enhanced and/or controlled host-guest associations may take place, leading to not only improved host-guest binding abilities but also fascinating properties.In this review, some representative contributions in the construction of controllable macrocyclic supramolecular assemblies in aqueous solution are presented with an emphasis on the stimuli-responsive control manner and wide applications of this property.展开更多
Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic s...Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic structure and modified functional groups of these macrocycles can influence substrate and transition state stability, as well as reaction selectivity. The inner cavities of these macrocycles are particularly beneficial, as they enable substrates to adopt preorganized arrangements and serve as versatile platforms for highly efficient supramolecular catalytic systems. This minireview provides an overview of recent advancements in supramolecular catalysis using various macrocycles, such as crown ethers, cyclodextrins,calixarenes, pillararenes, cucurbiturils, and other novel macrocycles.展开更多
Constructing more stable self-assembled organic nanotubes has been one of the focuses of scientists in recent decades.Hexakis(m-phenylene ethynylene)(m-PE)benzene macrocycles can form stable tubular self-assemblies in...Constructing more stable self-assembled organic nanotubes has been one of the focuses of scientists in recent decades.Hexakis(m-phenylene ethynylene)(m-PE)benzene macrocycles can form stable tubular self-assemblies in nonpolar or weakly polar solvents through theπ-πinteraction of the main skeleton and the hydrogen bonding of the side chain amide.We covalently linked two macrocyclic units at the para position of the macrocycles using two oligo(β-alanine)linkers through an efficient synthetic route.UV-visible spectroscopy,fluorescence spectroscopy,and circular dichroism spectroscopy were employed to demonstrate that the incorporation of two peptide chains significantly enhances the stability of the self-assemblies.Meanwhile,the average open time of the ion channel formed by the macrocyclic dimer in the lipid bilayer was significantly better than that of the ion channel formed by a single macrocycle.This study shows that this strategy effectively improves the efficiency of self-assembly and the stability of its formed self-assemblies,providing a feasible strategy for constructing organic self-assembled nanotubes in highly polar solvents.展开更多
The escalating challenges in water treatment,exacerbated by climate change,have catalyzed the emergence of innovative solutions.Novel adsorption separation and membrane filtration methodologies,achieved through molecu...The escalating challenges in water treatment,exacerbated by climate change,have catalyzed the emergence of innovative solutions.Novel adsorption separation and membrane filtration methodologies,achieved through molecular structure manipulation,are gaining traction in the environmental and energy sectors.Separation technologies,integral to both the chemical industry and everyday life,encompass concentration and purification processes.Macrocycles,recognized as porous materials,have been prevalent in water treatment due to their inherent benefits:stability,adaptability,and facile modification.These structures typically exhibit high selectivity and reversibility for specific ions or molecules,enhancing their efficacy in water purification processes.The progression of purification methods utilizing macrocyclic frameworks holds promise for improved adsorption separations,membrane filtrations,resource utilization,and broader water treatment applications.This review encapsulates the latest breakthroughs in macrocyclic host-guest chemistry,with a focus on adsorptive and membrane separations.The aim is to spotlight strategies for optimizing macrocycle designs and their subsequent implementation in environmental and energy endeavors,including desalination,elemental extraction,seawater energy harnessing,and sustainable extraction.Hopefully,this review can guide the design and functionality of macrocycles,offering a significantly promising pathway for pollutant removal and resource utilization.展开更多
文摘Welcome to this virtual special issue, which focuses on supramolecular/macrocyclic Chemistry. The beginnings of supramolecular chemistry can be traced back to 1967 with the identification of crown ethers by Pedersen [1], and being acknowledgement by the 1987 Nobel Prize to Lehn, Cram, and Pedersen for their leading discoveries in the host-guest systems [2]. Since these
基金supported by the Natural Science Foundation of Anhui Province Education Department(No.KJ2014A141,No.KJ2015A243,No.KJ2016A862)
文摘The construction of an unprecedented intertwined spiral solvent channel is driven by weak C–Cl…O and C–H…N interactions based on extraordinary parallel spirals which were structured from supramolecular synthon macrocycle 1（C44H44N4O4） with a propargylamine backbone. The product is characterized by ^1H NMR, ^13C NMR, IR and HRMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 28.922（3）, b = 8.5069（9）, c = 21.687（2）A^°, β = 130.6320（10）°, V = 4049.4（7） A^°3 and Z = 8. A total of 11874 reflections were collected, of which 4942 were independent（Rint = 0.0590） and 2937 were observed with I 〉 2σ（I）. The final full-matrix least-squares refinement gave R（I 〉 2s（I）） = 0.069 and w R = 0.167, S = 1.05,（Δρ）max = 0.20 and（Δρ）min =-0.22 e·A^1-3. The fluorescence of the product is discussed.
基金supported by the Royal Society(No.RGS\R2\202203Lan_4824933)the Engineering and Physical Sciences Research Council(Nos.EP/N509577/1,EP/T517793/1,and EP/S03305X/1).
文摘Enhancing the proton conductivity of proton exchange membranes(PEMs)is essential to expand the applications of proton exchange membrane fuel cells(PEMFCs).Inspired by the proton conduction mechanism of bacteriorhodopsin,cucurbit[n]urils(CB[n],where n is the number of glycoluril units,n=6,7,or 8)are introduced into sulfonated poly(ether ether ketone)(SPEEK)matrix to fabricate hybrid PEMs,employing a nature-inspired chemical engineering(NICE)methodology.The carbonyl groups of CB[n]act as proton-conducting sites,while the host–guest interaction between CB[n]and water molecules offers extra protonconducting pathways.Additionally,the molecular size of CB[n]aids in their dispersion within the SPEEK matrix,effectively bridging the unconnected proton-conducting sulfonic group domains within the SPEEK membrane.Consequently,all hybrid membranes exhibit significantly enhanced proton conductivity.Notably,the SPEEK membrane incorporating 1 wt.%CB[8](CB[8]/SPEEK-1%)demonstrates the highest proton conductivity of 198.0 mS·cm^(−1) at 60°C and 100%relative humidity(RH),which is 228%greater than that of the pure SPEEK membrane under the same conditions.Moreover,hybrid membranes exhibit superior fuel cell performance.The CB[8]/SPEEK-1%membrane achieves a maximum power density of 214 mW·cm^(−2),representing a 140%improvement over the pure SPEEK membrane(89 mW·cm^(−2))at 50°C and 100%RH.These findings serve as a foundation for constructing continuous proton-conducting pathways within membranes by utilizing supramolecular macrocycles as fuel cell electrolytes and in other applications.
基金supported by the National Natural Science Foundation of China (91527301, 21432004)
文摘A series of macrocycles, including crown ethers, cyclodextrins, calixarenes, pillararenes and cucurbiturils, are well known to be able to associate various organic/inorganic/biological guest molecules and ions in their well-defined cyclic cavities to form stable host-guest complexes and supramolecular systems through the cooperative contributions of various non-covalent interactions.When one or more functional groups are attached to the cavity of macrocycles or guest molecules, enhanced and/or controlled host-guest associations may take place, leading to not only improved host-guest binding abilities but also fascinating properties.In this review, some representative contributions in the construction of controllable macrocyclic supramolecular assemblies in aqueous solution are presented with an emphasis on the stimuli-responsive control manner and wide applications of this property.
基金the financial support from the Start-up Grant of Henan University of Technology (No.0004/31401509)the financial support from Distinguished University Professor grant (Nanyang Technological University)+1 种基金AcRF Tier 1 grants from the Ministry of Education of Singapore (Nos.RG107/19, RG11/20and RT14/20)the Agency for Science,Technology and Research (A*STAR) under its MTC Individual Research Grants (No.M21K2c0114)。
文摘Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic structure and modified functional groups of these macrocycles can influence substrate and transition state stability, as well as reaction selectivity. The inner cavities of these macrocycles are particularly beneficial, as they enable substrates to adopt preorganized arrangements and serve as versatile platforms for highly efficient supramolecular catalytic systems. This minireview provides an overview of recent advancements in supramolecular catalysis using various macrocycles, such as crown ethers, cyclodextrins,calixarenes, pillararenes, cucurbiturils, and other novel macrocycles.
基金the financial support by the National Natural Science Foundation of China(Nos.91227109 and 21778012 to Z.-L.Lu.,No.21801020 to R.Liu)Bohai University。
文摘Constructing more stable self-assembled organic nanotubes has been one of the focuses of scientists in recent decades.Hexakis(m-phenylene ethynylene)(m-PE)benzene macrocycles can form stable tubular self-assemblies in nonpolar or weakly polar solvents through theπ-πinteraction of the main skeleton and the hydrogen bonding of the side chain amide.We covalently linked two macrocyclic units at the para position of the macrocycles using two oligo(β-alanine)linkers through an efficient synthetic route.UV-visible spectroscopy,fluorescence spectroscopy,and circular dichroism spectroscopy were employed to demonstrate that the incorporation of two peptide chains significantly enhances the stability of the self-assemblies.Meanwhile,the average open time of the ion channel formed by the macrocyclic dimer in the lipid bilayer was significantly better than that of the ion channel formed by a single macrocycle.This study shows that this strategy effectively improves the efficiency of self-assembly and the stability of its formed self-assemblies,providing a feasible strategy for constructing organic self-assembled nanotubes in highly polar solvents.
基金supported by the National Key Research&Development Program(2022YFE0199800)National Natural Science Foundation of China(82104065,32061143045)+1 种基金Distinguished Young Research Project of Anhui Higher Education Institution(2022AH020035)Science and Technology Plans of Tianjin(22ZYJDSS00070).
文摘The escalating challenges in water treatment,exacerbated by climate change,have catalyzed the emergence of innovative solutions.Novel adsorption separation and membrane filtration methodologies,achieved through molecular structure manipulation,are gaining traction in the environmental and energy sectors.Separation technologies,integral to both the chemical industry and everyday life,encompass concentration and purification processes.Macrocycles,recognized as porous materials,have been prevalent in water treatment due to their inherent benefits:stability,adaptability,and facile modification.These structures typically exhibit high selectivity and reversibility for specific ions or molecules,enhancing their efficacy in water purification processes.The progression of purification methods utilizing macrocyclic frameworks holds promise for improved adsorption separations,membrane filtrations,resource utilization,and broader water treatment applications.This review encapsulates the latest breakthroughs in macrocyclic host-guest chemistry,with a focus on adsorptive and membrane separations.The aim is to spotlight strategies for optimizing macrocycle designs and their subsequent implementation in environmental and energy endeavors,including desalination,elemental extraction,seawater energy harnessing,and sustainable extraction.Hopefully,this review can guide the design and functionality of macrocycles,offering a significantly promising pathway for pollutant removal and resource utilization.
